Cdj)zco

ABSTRACT

CERTAIN 4-AMINO-3-OXAZOLINES HAVING HALOGENATED HYDROCARBON SUBSTITUENTS IN THE 2- AND 5-POSITIONS E.G., 4AMINO-2,2,5,5-TETRAKIS(TRIFLUOROMETHYL)-3-OXAZOLINE AND 4-AMINO-2-DIFLUOROMETHYL-6,6,7,7,8,8-HEXAFLUORO-2-TRIFLUOROMETHYL-3-AZA-1 -OXASPIRO(4,3)OCT-3-ENE AND THEIR TAUTOMERS, USEFUL AS PLASTICIZERS FOR POLYMERIC MATERIALS, AND THEIR PREPARATION, E.G., FROM REACTION OF A POLYHALOISOPROPYLIDENIMINE, E.G., PENTAFLUOROISOPROPYLIDENIMINE, AND A POLYHALOKETONE CYANHYDRIN, E.G., HEXAFLUOROCYCLOBUTANONE CYANHYDRIN, IN A POLAR SOLVENT AND IN THE PRESENCE OF A STRONGLY BASIC AMINE.

United States Patent Ofice Reissued June 1, 1971 Matter enclosed inheavy brackets [II appears in the original patent but forms no part ofthis reissue specification; matter printed in italics indicates theadditions made by reissue.

ABSTRACT OF THE DISCLOSURE Certain 4-amino-3-oxazolines havinghalogenated hydrocarbon substituents in the 2- and S-positions e.g., 4-amino-2,2,5,S-tetrakis(trifiuoromethyl)-3 oxazoline and4-amino-2-difiuoromethyl-6,6,7,7,8,S-hcxafluoro 2trifluoromethyl-3-aza-1-oxaspiro[4,3]oct-3 ene and their tautomers,useful as plasticizers for polymeric materials, and their preparation,e.g., from reaction of a polyhaloisopropylidenimine, e.g.,pentafluoroisopropylidenimine, and a polyhaloketone cyanhydrin, e.g.,hexafluorocyclobutanone cyanhydrin, in a polar solvent and in thepresence of a strongly basic amine.

RELATED APPLICATION This application is a continuation-in-part of mycoassigned copending application, Ser. No. 555,974, filed June 8, 1966,and now abandoned.

FIELD OF THE INVENTION This invention relates to, and has as itsprincipal objects provision of, novel 4-amino-3-oxazolines havinghalogenated hydrocarbon substituents in the 2- and S-positions and thepreparation of the same.

DETAILS OF THE INVENTION The novel compounds of this invention are4-amino- 3-oxazolines having halogenated hydrocarbon substituents in the2- and S-positions of the formula OFzX wherein:

X X X and X are alike or dilferent and are hydrogen, fluorine orchlorine, or X and X taken together can be perfiuoroalkylene having 1-2carbon atoms; R is hydrogen or alkyl or 1-4 carbons; and Y is hydrogen,alkyl of 1-4 carbons,

R being alkyl of 1-4 carbons or aryl, alkaryl, or aralkyl of 6-10carbons, and which alkyl and aryl radicals may be substituted with up tothree halogens (fluorine, chlorine, or bromine), and R being alkyl orcycl-oalkyl of up to 10 carbons; all with the proviso that the totalnumber of carbon atoms in R and Y together does not exceed 14.

More particularly, the compounds of this invention are the 3-oxazolinesof Formula I and their isomeric or tautomeric forms, the4-iminooxazolidines of the formula wherein R, Y and the Xs have themeanings given above; and selected salts and N-acyl and N-alkylderivatives of the amino and imino compounds of Formulas I and II.

Compounds of the above Formulas I and II in which R is hydrogen and theX5 and Y are as previously defined are tautomers and exist in tautomericequilibrium, especially in solution, as shown by the following formulas:

Consequently, when one tautomer is mentioned in this application, it isintended that the other also be included. As would be expected from thistautomeric equilibrium involving a mobile proton, these compounds havemarked acidic properties. For example, this hydrogen will exchangerapidly with deuterium when D 0 is added to an acetone solution of thecompound, as evidence by the disappearance of the NH absorption band inthe nuclear magnetic resonance spectrum.

In the special case of4-amino-2,2,5,5-tetrakis(trifluoromethyl)-3-oxazoline, in 'which both Rand Y are H, only a single absorption band is observed from the twoprotons in the n.m.r. spectrum at room temperature; and they bothexchange rapidly with D 0.

Since compounds of types I and II in which R is H exhibit acidicproperties, they can form salts with bases. The salts from eithertautomer are identical, for their anions can be represented by thefollowing resonance For example,4-amino-2,2,5,S-tetrakis(trifiuoromethyl)-3- oxazoline (R and Y are H,and the Xs are P) is a weak acid. It can be titrated with a strong base,such as tetramethyl amomnium hydroxide, in a nonaqueous solvent such asacetone or pyridine, to give a sharp end-point. The salt formed in thistitration can be represented by the resonance structures:

4-acetylamino-2,2,5,5 tetrakis (trifiuoromethyl) 3- oxazoline (R is H, Yis CH CO) is a stronger acid. It

can be titrated in water with sodium hydroxide to give a salt that canbe represented by the resonance structures:

Compounds of the above Formulas I and II in which neither R nor Y is Hexist as isomeric structures similar to types I and II above. Either oneor both types of these compounds can be prepared in a single reaction bycausing a tautomeric mixture, in which R is H or R and Y both are H, toreact with an alkylating or acylating reagent. For example, dimethylderivatives (where R and Y are CH corresponding to type I and to type IIcan both be prepared in a single reaction by treating 4-amino-2,2,5,5-getrakisfirifluoromethyl)-3-oxazoline with dimethyl sulate.

The present novel compounds of Formulas I and II, wherein Y is H, andwhich serve as precursors for the remaining compounds of Formulas I andII, are prepared by the reaction of one mole of a salt of apolyhaloketone cyanhydrin having the formula wherein M is an alkalimetal or an amine and X and X are as defined previously, with one moleof a polyhaloisopropylidcnimine of the formula NH X"CF2-ilCF-X wherein Xand X are as defined previously. The reaction is preferably carried outin the presence of an inert, polar, reaction medium, preferably organic,such as dimethylformamide; dimethyl sulfoxide; liquid nitriles, e.g.,acetonitrile and benzonitrile; glycol ethers, e.g., the dimethyl ethersof ethylene and diethylene glycols; etc., although the reaction can becarried out without added solvent.

In one embodiment of the above process, the compounds of Formula I orII, where Y is hydrogen, are prepared in two steps. The first stepconsists of treating a polyhaloketone of the formula v in which X and Xare as previously defined, with an alkali metal cyanide, such as sodiumcyanide or potassium cyanide, preferably in the presence of a polarsolvent such as dimethylformamide, acetonitrile, dirnethyl sulfoxide, ordiethylene glycol dimethyl ether (diglyme), at a temperature of from 50to 100 C. to form an alkali metal salt of the ketone cyanhydrin (comparemy US. Patent No. 3,310,570). The salt of the ketone cyanhydrin can beisolated, if desired, by cooling the reaction mixture from this firststep to room temperature, filtering and evaporating the filtrate todryness under reduced pres- 4 sue. However, it is not necessary toisolate the salt before carrying out the second step of the process asdescribed below.

The second step consists of treating the cyanohydrin salt with an irnineof Formula IV above; acidifying the resulting reaction mixture; and thenpurifying the product oxazolines and/or tautomeric oxamlidines byconventional means such as sublimation, distillation, orrecrystallization.

In a second embodiment of the process for making the compounds of thisinvention, compounds of Formulas I and II, where the Xs are hydrogen,are prepared by reaction of equimolar amounts of apolyhaloisopropylidenimine of Formula IV with a polyhaloaoetonecyanhydrin of the following formula:

wherein X and X are hydrogen, in the presence of a strongly basic aminee.g., piperidine, triethylamine, diethylamine, or pyrrolidine, andpreferably in an inert polar reaction medium of the types describedpreviously, at ordinary or ambient temperatures. An exothermic reactiontakes place which is usually complete in one to four days.

The reaction mixture is mixed with an equal volume of water andneutralized with a dilute inorganic acid, e.g., 10% hydrochloric acid.The resulting product oxazoline (and/or the tautomeric oxazolidine) isprecipitated by dilution of the reaction mixture with water, and theprecipitate is purified by conventional means such as recrystallizationand sublimation.

The compounds of the invention of Formulas I and II in which R and/or Yis other than hydrogen can be prepared from those in which both R and Yare hydrogen, or the alkali metal salts of these latter compounds, bytreatment with conventional alkylating or acylating agents. Theresulting derivatives are also novel compounds which are useful forvarious purposes. The reaction can be carried out by contacting theoxazolines or oxazolidines (Formula I or II, where R=Y=H), or theiralkali metal salts, with the alkylating or acylating reagents, withoutsolvent or in the presence of an inert solvent, at a temperature from 0to 200 C., and isolation of the product by conventional means, such asdistillation, recrystallization, or sublimation.

The alkylated derivatives are the compounds of Formulas I and II inwhich either R or Y or both are alkyl groups of 1-4 carbon atoms.Suitable alkylating reagents include alkyl sulfates,p-toluenesulfonates, and halides in which the alkyl moieties have 1-4carbon atoms.

The acylated derivatives are the compounds of the above Formulas I andII in which Y is The compounds where Y is are prepared by treating acompound of the above general Formula I or II, where Y is H, with anacyl halide,

ll R CX where R is as defined hereinbefore and X is fluorine, chlorineor bromine, at elevated temperatures, e.g., 200- 250 C., for severalhours, e.g., 4-30 hours. The resulting solid acyl derivatives can beisolated from the reaction mixture by filtration and purified, ifdesired, by recrystallization.

The acylated derivatives in which Y is are prepared in two steps. In thefirst step, a compound of Formula I, where Y and R are both H, isreacted with oxalyl chloride to form a 4-isocyanato-2,2,5,5-tetrakis-(polyhalomethyl)-3-oxazoline. In the second step, the isocyanatoderivative is further reacted with an alcohol, HOR, where R is definedas above. The resulting solid urethane can be isolated from the reactionmixture by filtration, and purified if desired by recrystallization.

The polyhaloketones of Formula V, in which the Xs are hydrogen, fluorineor chlorine, or in which X and X taken together, are

where a is 1 or 2, used in preparing the compounds of this invention arewell-known materials shown, for example, in Lovelace, Rausch andPostelnek, Aliphatic Fluorine Compounds, pages 190-192, ReinholdPublishing Corp., New York (1958).

The polyfluoroketone cyanhydrin reactant for the second processembodiment described above can be prepared by reaction of apolyfiuoroketone of Formula V with an equimolar amount of hydrogencyanide in the presence of piperidine as catalyst. The reaction can becarried out in the absence of added solvent, or, if desired, in thepresence of an inert solvent such as acetonitrile. The reaction iscomplete by the end of the addition of the reactants, and the desiredpolyfluoroketone cyanhydrin can be isolated from the reaction mixture bydistillation after removal of piperidine catalyst by treatment with anequivalent of p-toluenesulfonic acid.

The polyhaloisopropylidenimine reactants of Formula IV in which the Xsare fluorine or chlorine can be obtained by reacting a polyfluoroketoneof Formula V in which the Xs are fluorine or chlorine with at least onemolar equivalent of ammonia at -50 to C. followed by dehydration of theresulting aminohydroxy polyhaloaikane with a dehydrating agent in thepresence of an acid acceptor, and then distilling to recover the imine.The imine reactant also may be prepared by reacting hydrazoic acid witha polyhalothioketone. Both of the aforesaid preparatory methods for thepolyhaloalkylidenimine are disclosed and claimed in US. Patent No.3,226,439, and described in J. Org. Chem. 30, 1398 (1965).

The imines of Formula IV in which X and/or X are hydrogen can be made bya modification of the method of Zeifman et a1., Akad. nauk S.S.S.R.Doklady 153, 1334 (1963), for preparing hexafiuoroisopropylidenimine.The process comprises first reacting the corresponding ketone withphenyl isocyanate in an autoclave at about 200 C. employing atriarylphosphine oxide catalyst to form the anil, i.e., the N-phenylderivative of the imine. Then the anil is condensed with ammonia atambient temperature, and aniline is split out thermally or with a strongacid such as phosphorus pentoxide to give the imine (Middleton, U.S.Patent No. 3,342,864).

EMBODIMENTS OF THE INVENTION There follow some nonlimiting examplesillustrating the compounds and processes of the invention in moredetail. Unless otherwise mentioned, temperatures and pressures in theseexamples were ambient. It will be noted that ring carbons are, in mostcases, omitted from structural formulas.

EXAMPLE 1 Hexafiuoroacetone, 25 ml. at -78 C. (ca. 0.25 mole), wasslowly distilled over a period of 30 minutes into a stirred suspensionof 12.25 g. (0.25 mole) of powdered sodium cyanide in 200 ml. ofacetonitrile. The temperature of the reaction rose spontaneously to 60C. The reaction mixture was stirred for an additional 30 minutes, andthen cooled to 25 C. Hexafluoroisopropylidenimine, 27 ml. at 10 C. (ca.0.25 mole), was then distilled into the reaction mixture, and themixture was stirred for 3 days at room temperature. An equal volume ofwater was added, and the mixture was neutralized with 10% aqueoushydrochloric acid. The organic layer that formed was separated andshaken with water until a solid formed. The solid was collected on afilter, washed with water, recrystallized from benzene, and thensublimed at 10 mm. and 130 C. to give 33.0 g. (37% yield) of 4-amino-2,2,5,5-tetrakis(trifiuoromethyl)-3-oxazoline as colorless crystals,M.P. 136-138" C. (sealed capillary). The infrared spectrum showed a bandat 5.89 The H n.m.r. spectrum in (CD CO at 25 C. showed a broad singletat 7.66 p.p.m., and at S0 C. showed two singlets of equal area at 8.00and 8.75 p.p.m. lower field from (CH Si. The F n.m.r. spectrum in (CD SOshowed two septets (1:5.9 c.p.s.) centered at 72.0 and 77.1 p.p.m.higher field from trichlorofiuoromethane.

Analysis.Calcd, for C H F N O: C, 23.47; H, 0.56; F, 63.67; N, 7.83.Found: C, 2388-; H, 0.77; F, 64.11; N, 7.89.

EXAMPLE 2 4-amino-2,2,5,5-tetrakis (trifluoromethyl) -3 -oxazoline (X =X=X =X =F; R=Y=H) and/or tautomer Hexafluoroisopropylidenimine, 76 ml.(ca. 0.7 mole), F, 63.67; N, 7.83. Found: C, 23.88; H, 0.77; F, 64.11;g. (0.67 mole) of hexafluoroacetone cyanhydrin in 100 ml. ofacetonitrile. The solution was stirred at room temperature for 3 days.An equal volume of water was added and the solution neutralized with 10%hydrochloric acid. The organic and aqueous layers were separated. Waterwas added to the organic layer causing crystallization. The crystalswere collected, on a filter, washed with water, recrystallized frombenzene, and sublimed at C. and 10 mm. to give 88.9 g. (58.4% yield) of4 amino-2,2,5,5-tetrakis(trifiuoromethyl)-3- oxazoline melting at136-138 C.

The F n.m.r. spectrum in (CD3)2CO showed multiplets at 73.7 p.p.m. and78.4 p.p.m.

Analysis.Calcd. for C F N H O: C, 23.67; H, 0.56; F, 63.67; N, 7.83.Found: C, 23.43; H, 0.75; F, 63.49; N, 7.90.

7 EXAMPLE 3 4-amino-2,2-bis (trifluoromethyl)-5-ch1orodifluoromethyl-S-difluoromethyl-3-oxazoline NH 0 NON one! 1 org CF a oFm-il-cmci omrr- CN 3 NH; CFzCl 0% and/or tantomer CF: CF;

1-chloro-1,1,3,3-tetrafluoroacetone, 16.5 g. (0.1 mole), was addeddropwise over 30 minutes to a stirred suspension of 4.9 g. (0.1 mole) ofpowdered sodium cyanide in 75 ml. of dimethylformamide cooled to 0 C.The reaction mixture was stirred at 0 to 10 C. for 2 hours, and then 11ml. at 10 C. (ca. 0.1 mole) of hexafluoroisopropylidenimine wasdistilled into the reaction mixture. The mixture warmed spontaneously to40 C. The mixture was cooled and poured into 250 ml. of 10% hydrochloricacid, and the oil that separated was collected and washed with water,and then dissolved in ml. of 20% fuming sulfuric acid. This solution waspoured over ice, and the solid that formed was collected on a filter,washed with water, dried in a desiccator over phosphorus pentoxide, andthen sublimed at 100 C. and 10 mm. to give 10.4 g. of4-amino-2,2-bis(trifluoromethyl)-5-chlorodifluoromethyl-5-difluoromethyl-3-oxazolineas a white crystalline powder, M.P. 10l103 C. The H n.m.r. spectrum in(CDQ CO showed a triplet (J =52 c.p.s.) to a triplet (J=0.7 c.p.s.)centered at 4.57 p.p.m. (1H) and a broad singlet centered at 5.5 p.p.m.(2H) from (CH Si. The infrared spectrum showed a band at 5.91 1.

Ana1ysis.Calcd. for c,H,c1F,,N,o= C, 23.58; H, 0.85; Cl, 9.93; F, 53.29;N, 7.86. Found: C, 23.87; H, 1.27; C], 9.72; F, 53.58; N, 7.90.

EXAMPLE 4 4'amino-2-chl0rodifluoromethy1-2,5,5-tris(trifluoromethyl)-3-oxazoline ONa NHz

and/or tautomer Hexafluoroacetone, 10 ml. at 78 C. (0.1 mole), wasslowly distilled over a period of minutes into a stirred suspension of4.9 g. (0.1 mole) of powdered sodium cyanide in 100 ml. of acetonitrile.The reaction mixture was stirred at 25 C. for 2 hours, and 18.2 g. (0.1mole) of chloropentafluoroisopropylidenimine was added dropwise thereto.Stirring was continued for 2 days, and then the mixture was poured into200 ml. of 10% hydrochloric acid. The organic layer that separated waswashed with water until it solidified. The solid was dried in vacuumover phosphorus pentoxide, and sublimed at 100 C. (10 mm.) to give 11.9g. (32%) of4-amino-2-chlorodifluoromethyl-2,5,5-tris(trifluoromethyl)-3-oxazolineas a white, crystalline solid, M.P. 103-104 C.

Analysis.-Calcd. for CqHgClFuNgOZ C, 22.44; H,

8 0,54; Cl, 9.47; F, 55.80; N, 7.48. Found: C, 23.23; H, 0,54; Cl,10.24; F, 55.80; N, 8.00.

cmH g u NaCH 1 1. omcF1 NH: CF; l cran O -c a and/or tautomerPentafluoroacetone, 22 ml. (ca. 0.25 mole), at -78 C. was slowlydistilled into a stirred suspension of 12.25 g. (0.25 mole) of powderedsodium cyanide in 200 ml. of acetonitrile. The temperature of thereaction rose spontaneously to 45 C. The reaction mixture was stirred anadditional 30 minutes, cooled to 25 C., and filtered.Hexafiuoroisopropylidenimine, 27 ml. at 10 C. (ca. 0.25 mole), wasdistilled into the reaction solution, and the solution was stirred atroom temperature for 3 days. An equal volume of water was added, and thesolution was neutralized with 10% aqueous hydrochloric acid. Thesolution was concentrated, and the crystals that formed were collectedon a filter, washed with water, recrystallized from benzene and sublimedat 10 mm. and 130 C. to give 17.9 g. (23% yield) of4-amin0-2,2,5-tris(trifluoromethyl)-5-difluoromethyl)-3-oxazoline, M.P.123- 125 C. The infrared spectrum showed bands at 3;, 5.86;, and 6.22and a strong absorption in the 8 to 101.0 region. The H n.m.r. spectrumin (CD MCO showed a triplet (J=51.5 c.p.s.) centered at 6.01 p.p.m. anda broad singlet at 7.08 p.p.m. The F n.m.r. spectrum in (CD CO showed adoublet (1 =52 c.p.s.) split to multiplets at 131.3 p.p.m. (CF H), andmultiplets centered at 73.5 p.p.m. cm and at 78.8 p.p.m. 2cF,

Analysis.-Calcd. for C6H3F11N2OI C, 24.73; H, 0.89; F, 61.45; N, 8.23.Found: C, 24.59; H, 1.17; F, 61.60; N, 8.27.

EXAMPLE 6 and/or tautomer Pentafluoroacetone, 8 ml. (ca. 0.09 mole), wasslowly distilled into a suspension of 4.4 g. (0.09 mole) of powderedsodium cyanide in 75 ml. of acetonitrile. The temperature of thereaction rose spontaneously to 54 C. The mixture was stirred for anadditional 2 hours and filtered. To the solution was added dropwise 13g. (0.09 mole) of pentafluoroisopropylidenimine. The solution wasstirred at room temperature for 3 days. An equal volume of water wasadded, and the solution was neutralized with 10% aqueous hydrochloricacid. The solution was concentrated, the crystals that formed werecollected on a filter, washed with water, recrystallized from benzene,and sublimed at 10 mm. and 130 C. to give 12.7 g. (45% yield) of4-amino-2,5-bis(trifiuoromethyl)-2,5-bis(difluoromethyl)-3-oxazoline,M.P. 133--135 C. The infrared spectrum showed bands at 3 1. and 5.92 andstrong absorption in the 8 to 10 region. The H n.m.r. spectrum in (CD COshowed a triplet (J=55 c.p.s.) at 5.65 p.p.m. (CF H), a triplet (J=54c.p.s.) at 6.10 p.p.m. (CF H), and a ver broad signal at 6.5 p.p.m. (NHThe F n.m.r. spectrum in (CD -CO showed multiplets centered at 73.8p.p.m. (CF at 78.5 p.p.m. (CF and at 132.2 p.p.m. (ZCF H).

Analysis.-Calcd. for CqH4F10N20: C, 26.13; H, 1.25; F, 58.98. Found: C,26.34; H, 1.54; F, 59.88.

EXAMPLE 7 4-amino-2,5,5-tris(trifluoromethyl)-2-difluoromethyl-3-oxazoline and or tautomer Hexafiuoroacetone, ml. (ca. 0.09 mole), wasslowly distilled into a suspension of 44 g. (0.09 mole) of powderedsodium cyanide in 75 ml. of acetonitrile. The temperature of thereaction rose spontaneously to 56 C. The mixture was stirred for anadditional 30 minutes and then filtered. Pentafiuoroisopropylidenimine,13 g. (0.09 mole), was added dropwise, and the solution was stirred atroom temperature for 3 days. An equal volume of water was added, and thesolution was neutralized with 10% aqueous hydrochloric acid. Thesolution was concentrated, the crystals that formed were collected on afilter, washed with water, recrystallized from benzene, sublimed at 10mm. and 130 C. and recrystallized from benzene again to give 12.9 g.(44% yield) of 4-amino- 2,5,5-tris(trifluoromethyl)2-difluoromethyl-3-oxazo1ine, M.P. 130-132 C. The infrared spectrumshowed bands at 3 and 5.92 and strong absorption in the 8 to 10p.region. [The H n.m.r. spectrum in (CD CO showed a triplet (1:53 c.p.s.)at 5.90 p.p.m. (CF H), and a broad singlet at 6.35 p.p.m. The F n.m.r.spectrum in (CD CO showed multiplets centered at 132.1 p.p.m. (CF H),78.7 p.p.m. (CF and 73.9 p.p.m. (2CF Analysis.Oalcd. for C H F N O: C,24.72; H, 0.89; F, 61.45. Found: C, 24.98; H, 1.48; F, 61.28.

EXAMPLE 8 4-amino-2,2-bis (trifluoromethyl -5,5-bis (difluoromethyl-3-oxazoline and or tautomer Tetrafluoroacetone, 11.7 g. (0.09 mole),was added dropwise to a suspension of 4.4 g. (0.09 mole) of powderedsodium cyanide in 75 ml. of acetonitrile. The temperature rosespontaneously to 61 C. during the addition. The reaction mixture wasstirred at room temperature overnight and filtered to remove theunreacted sodium cyanide. Hexafiuoroisopropylidenimine, 9.7 ml. (ca.0.09 mole), was bubbled into the solution and the solution was stirredat room temperature for 3 days. An equal volume of water was added andthe solution neutralized with 10% hydrochloric acid. The solution wasconcentrated on a steam bath and crystallized. The crystals were washedwith water, recrystallized from benzene, and sublimed at C. and 10 mm.to give a mixture (4.2 g.) of the desired product and4-oxo-2,2,5,5-tetrakis- (difluoromethyl)oxazolidine. This solid productwas treated with 10% sodium hydroxide solution and filtered to removethe 4-oxo-2,2,5,5-tetrakis(difiuoromethyl)oxazolidine, which is solublein dilute alkali. The insoluble residue was dried and then sublimed atC. and 10 mm. to give 3.2 g. (7.3% yield) of4-amino-2,2-bis(trifluoromethyl)-5,5-bis(difiuoromethyl) 3 oxazoline[melting at 108-110 C.]

The F n.m.r. spectrum in (CDQ CO showed a multiplet at 79.1 p.p.m. and adoublet (J=54 c.p.s.) split to multiplets centered at 130.9 p.p.m. The Hn.m.r. spectrum in (CD CO showed a triplet (1:54 c.p.s. centered at 'r4.08 and a broad singlet at T 3.17 (NH Analysis.Calcd. for C F N H O: C,26.10; H, 1.25; N, 8.69; F, 58.99. Found: C, 26.02; H, 1.29; N, 8.71; F,58.94.

EXAMPLE 9 4-amino-2,2,5-tris difluoromethyl -5-trifiuoromethyl-3-oxazoline -C F H and/or tautomor C F H1,1,3,3-tetrafiuoroisopropylidenimine, 6.6 g. (0.05 mole), was addeddrop wise to a solution of 8.9 g. (0.05 mole) of pentafluoroacetonecyanohydrin and 2 ml. (0.02 mole) of piperidine in 15 ml. ofacetonitrile. The solution was stirred at room temperature for 4 days.An equal volume of water was then added and the solution neutralizedwith 10% hydrochloric acid. The crystals that formed were collected on afilter, washed with water, washed with 10% sodium hydroxide, andsublimed at 130 C. and 10 mm. to give 3.19 g. (29% yield) of 4- amino2,2,5 tris(difiuoromethyl)-5-(trifiuoromethyl)- 3-oxazoline melting at9092 C. The H n.m.r. in (CD CO showed peaks in the 2.80 to 5.001-region. [The F n.m.r. (CD CO showed multiplets at 73.8 p.p.m. (CF;,) andmultiplets over 400 cycles centered at 132 p.p.m. (3CF H).] Infrared:2.86 1, 2.92 1, 2.98 1, 3.15;). and 6.19 1. for NH 5.88;; for C=N.

Analysis.Calcd. for C F H N O: C, 27.64; F, 56.22; H, 1.66; N, 9.21.Found: C, 27.54; IF, 55.69; H, 2.06;] N. 9.40.

EXAMPLE 10 4-amino-2,2-bis(difiuoromethyl -5,5-bis(trifiuoromethyl3-oxazoline C FgH 1,1,3,3-tetrafiuoroisopropylidenimine, 6.5 g. (0.05mole), was added dropwise to a solution of 9.5 g. (0.05 mole) ofhexafluoroacetone cyanohydrin and 2 ml. (0.02 mole) of piperidine in 15ml. of acetonitrile. The solution was stirred at room temperature for 4days. An equal volume of water was then added and the solutionneutralized with 10% hydrochloric acid. The crystals that formed werecollected on a filter, washed with 10% sodium hydroxide, and sublimed at130 C. and 5 mm. to give 2.90 g. (18% yield) of4-amino-2,2-bis(difluoromethyl) -5,5-bis (trifiuoromethyl) -3-oxazolinemelting at IDS-108 C. The H n.m.r. in (CD C showed a triplet (1:54c.p.s.) centered at 4.15r (201 1 1) and a broad singlet at 4.371- (NH[The F n.m.r. in (CD C0 showed multiplets at 65.1 p.p.m. (2CF andmultiplets centered at 131.9 p.p.m. (2CF H).] Infrared: Infrarad: 287p,3.05s, and 3.16 1. for NH;; 5.90;t for -C=N.

Aualysis.-Calcd. for CgF1uH4N2O: C, 26.09; F, 58.99; H, 51.26; N, 8.69.Found: C, 26.50; F, 58.94; H, 1.70; N, 8.7

EXAMPLE 114-amino-2,5,5-tris(difiuoromethyl)-2-trifluoromethyl-S-oxazoline and/ortautomer 1,1,3,3-tetrafiuoroacetone, 15 g. (0.12 mole), was addeddropwise to a suspension of 4.9 g. (0.12 mole) of powdered sodiumcyanide in 75 ml. of acetonitrile. During the addition, the temperaturerose spontaneously to 70 C. The mixture was stirred for 30 minutes andfiltered. Pentafluoroisopropylidenimine, 16.9 g. (0.1 mole), was thenadded dropwise to the filtrate. The temperature rose spontaneously to 50C. during the addition. The solution was stirred at room temperature for4 days, An equal volume of water was added and the solution wasneutralized with 10% hydrochloric acid. The aqueous and organic layerswere separated and the organic layer was extracted with water. Theaqueous layers were combined and distilled. The fraction boiling at 98C. partially solidified. The solid was collected on a filter, washedwith 10% sodium hydroxide, and recrystallized from benzene to give 3.39g. [(97% yield)] of 4-amino-2,5,5-tris(difiuoromethyl)Z-trifluoromethyl- 3-oxazoline melting at l29-l3l C. The H n.m.r. in (CDS0 showed a singlet at 'r 6.7 (NH a triplet (1:53 c.p.s.) centered at 1-3.58 (2H), and a triplet (J=53 c.p.s.) centered at 1' 3.91 (1H).Infrared: 5.90; for C=N.

Analysis.-Calcd. for C F H N O: C, 27.63; F, 56.21; H, 1.65; N, 9.26.Found: [C, 27.82;] F, 55.91; [H, 1.72;] N, 9.90.

EXAMPLE 12 4-amino-2-difluoromethyl-6,6,7 ,7,8,8-hexafluoro-2-trifluoromethyl-3-aza-1-oxaspiro[4,3]oct-3-ene and/0rtautoma Hexafiuorocyclobutanone, 36 ml., was added to 24 ml. of hydrogencyanide and 1 ml. of piperidine at -l0 to 0 C. After standing overnightat ca. 25 C., the mixture was distilled to give hexafiuorocyclobutaonecyanhydrin, B.P. 63 C./20- mm.

Pentafluoroisopropylidenimine, 5 g. (0.03 mole), was added dropwise to asolution of 7 g. (0.03 mole) of hexafiuorocyclobutanoue cyanhydrin and 2ml. of piperidine in 15 ml. of acetonitrile. The solution was stirred atroom temperature for 3 days. An equal volume of Water was added and thesolution was neutralized with 10% hydrochloric acid. The organic andaqueous layers were separated, The crystals that formed in the organiclayer were collected on a filter, washed with water, and sublimed at C.and 10 mm. to give 3.39 g. (32% yield) of4-amino-2-difiuoromethyl-6,6,7,7,8,8-hexafiu0ro-2-trifluoromethyl-3-aza-l-oxaspiro[4,31oct-3-ene as colorless crystalsmelting at l12-ll5 C. Recrystallization of a portion of this materialfrom benzene raised the melting point to l25.6-l26.0 C. The H n.m.r. in(CD CO showed a triplet (1:53 c.p.s.) centered at 1 4.22 (CF H) and abroad region at 1- 3.41 (NHQ), The F n.m.r. in (CD CO showed doublets(1:53 c.p.s.) split to multiplets at 136.5 p.p.m, (CF l-l), multipletsat 128.4, 130.4, and 134.8 p.p.m. (6F), and a triplet (1:7 c.p.s.) splitto doublets (1:2 c.p.s.) at 81.2 p.p.m. (CF Infrared: 2.84 2.97 3.03;,3.15 for NHg; 5.87 for C:N.

Analysis.Calcd. for C F H N O: C, 27.28; F, 59.35; H, 0.86; N, 7.95.Found: C, 27.65; F, 58.44; H, 0.89; N, 7.78.

EXAMPLE 13 4-amino-2,2-bis(trifluoromethyl)-6,6,7,7,8,8-hexafluoro-3-aza-1-oxaspiro[4,3loct-3-eneandjor tautomcr Hexafluoroisopropylidenirnine, 5 ml. (ca, 0.03 mole),was bubbled into a solution of 7 g. (00.3 mole) of hexa- 13fluorocyclobutanone cyanhydrin and 2 ml. (0.02 mole) of piperidine in 15ml. of acetonitrile. The solution was stirred at room temperature for 4days. An equal volume of water was then added and the solution wasneutralized with 10% hydrochloric acid. The crystals that formed werecollected on a filter, washed with Water, washed with 10% sodiumhydroxide, and sublimed at 130 C. and 10 mm, to give 6.51 g. (58% yield)of 4-amino-2,2- his(trifluoromethyl)-6,6,7,7,8,8hexafiuoro-S-aza-l-oxaspiro[4,3]oct-3-ene melting at 135137 C. The Hn.m.r. in (CD CO showed a broad singlet at 2.52-r. The F n.m.r. in (CDCO showed a multiplet at 82.1

TABLE I Reactants Product oxazoll lies Ketone Cyanide Imine (ortautorner) 0 KCN NH NH: n 11 OF;,CCF3 ClCFz-C-CFC1 N or, I 01 201 CFzClI NaCN I IH I IHQ CICFzC-CF CI OF3CCF3 01cm or,

(5 NaCN I IH r ms 010134-01", om-d-omH CF Cl CF;

CFZH

KCN nt I irn ClCFr-C-CFzCl mom-(Lorna CFZCK CFzCl I cmcl one! l NaCN I HIIIHz noFz-c-cnu rrcrz-h-cmn Ircr I CFzH CFnH 1i NaCN 1 IH rm CF or O CF-(J-CF; 2- I F I 20 F org-or, I or, F: CF1

0 KCN NH NH: i H01 2% CFII I 2 2 F20 N F20 CF: CF'H I 2 CF;

0 NaCN IfilH r m.

F20 CFz-CFg I or, F2 CF:

CFzH

0 NaCN NH NH: ("1 CF CF (11 3 2 F20 N F20 or, CF

1 5 EXAMPLE l4 4-acetylamino-2,2,5,S-tetrakis (trifluoromethyD-3- 16from ethanol. There was obtained 3.1 g. of 4-acetylamino- 2,2,5,5tetrakis(trifiuoromethyl)-3-oxazoline as colorless needles, M.P. 189-190C. (sealed capillary). The H oxazolme n.m.r. spectrum in (CD3)2 Showed asiflglfit at -C i) 5 p.p.m. (3H) and a. broad peak at 10.3 p.p.m. (1H)from A) (CH Si. The infrared spectrum showed bands at 5.77 O and 6.04The ultraviolet spectrum in ethanol showed NH ll A 222 m and A 262 mu.The 262 mp. absorption CF F f increased as the sample was diluted.

3 0 C 3 10 Analysis.-Ca1cd. for C H F N O C, 27.01; H, 1.01; CF: L P CF:I 1;,851698; N, 7.70 Found: C, 27.38; H, 1.30; F, 56.92, N, Thefollowing list of specific 4-acylamino-3-oxazolines CF: CF: (or theirtautomeric acyliminooxazolidines), in which and/or tautomer 0 o Amixture of 6.3 g. of 4-amino-2,2,5,5-tetrakis(trifluo- Y }5 (UJ R1romethyl)-3-oxazoline and 25 ml. of acetyl chloride was heated in an80-ml. Hastelloy C bomb at 200 C. for and the reactants from which theyare prepared as by 8 hours. The bomb was cooled and vented, and the sus-O essentially the procedure of Example 14 are listed in pended solid wascollected on a filter and recrystallized Table II:

TABLE II Reaetants Products 4-aeylamlno-3-oxazollne (or4-amino-3-oxazoline (or tautomer) Acyl halide tautomers NHz CIHifiBXCFzCl 0 HNCCzHs CF20] ch01 N CF20]. OFiCl 1 u ch01 0 IINCC3H1 N CF10!GFZH I N i CFzH CF51 O-xCF:

IIIH: CARE-I101 0 CF; 0 HNECiHt OFa F 2H 0 C FzH CFzH NI|I2 CFaIIJF (H)HNCCF (CFa)zl l a (OFa) 0 (0F3)l O (CFa)! IFIH: (M15001 HIIT- ]%C|Hl(0mm, N (CFQHa O--(CF:H)2 O- -(CFzE):

NH: CFzOl f O cmoi g 0-CF2C1 0 0mm F:

TABLE II-Continued Reaetants -amino-B-oxazoline (or tautomer) Acylhalide (Chirp;

tautom Products, 4-a/cylamino-3-oxazoline (or FzH O- i-CFa IFH 01 01 Qti-M3 CF20 l 01 0 CF: Cl 0 OFzCl i F101 CFa CFzCl 17H: ClH gCHZfiCl 0 HNiJCHzCo a (CF a)2 NH: (I) (H) mm-Q-dct HN-CC:Hs (CF2H) 1 (OF H) oLtor'zmi 2 0 (OF2H) NH; 0113001 CF2 l H IINCCH; F /CF2 l CF20 CF F,(: aon F211 O-CF3 CFzH NH: CsHsCCl CFa I II I O HNCCQH! F2C\ /CF2 CF20 I CFF20\ 3 CFz I FlH -OF3 CFzH EXAMPLE l5 and then poured into 200 ml. ofwater. The organic layer 4-methylaminoand4-dimethy1amino-2,2,5,5-tetrakis trifiuoromethyl -3-oxazoline wascollected in 50 ml. of ether, and the ether solution was washed withwater and dried over magnesium sulfate. Distillation gave two mainfractions. The lower boiling fraction, 6.2 g., B.P. 8890 C. (50 mm.),solidified upon cooling. Recrystallization from pentane gave 4.1 g. of4- methylamino-2,2,5,5-tetrakis(trifiuoromethyl)-3-oxazoline ascolorless crystals, M.P. 59.560.5 C. The infrared spectrum showed a bandat 596 The H n.m.r. spectrum in (CD CO showed a broad signal at 1- 2.25(NH) and a doublet (J=4.7) at 1- 6.88 (CH that goes to a singlet uponthe addition of D 0. The F n.m.r. spectrum showed two septets (1:5.8)centered at 72.3 and 77.2 p.p.m. from trichlorofluoromethane.

Analysis.-Calcd. for C H F N O: C, 25.82; H, 1.08; F, 61.27; N, 7.53.Found: C, 25.58; H, 1.21; F, 61.23; N, 7.25.

The higher boiling fraction, 4.9 g., B.P. 92-92.5 C. (50 mm), wasfurther purified by cooling to 10 C., filtering off the precipitatedsolid, and redistilling the filtrate to give 2.7 g. of4-dimethylamino-2,2,5,5-tetrakis (trifluoromethyl)-3-oxazoline as acolorless liquid, B.P. 92 C. (50 mm.); n 1.3460. The infrared spectrumshowed a band at 6.07 The H n.m.r. spectrum of a neat sample showed asinglet at 'r 6.84, and the F spectrum 4-methylamino-2,5 ,5 -tris (triiluoromethyl -2-difluoromethyl-3-oxazoline (X =X=X =F; X =H; R=-CH Y=H)NH, H1? CH:

Methyl iodide, 20.8 g. (0.14 mole), was added dropwise to a solution of22 g. (0.07 mole) of 4-amino- 2,5,5-tris(trifluoromethyl 2diflnoromethyl 3 oxa- 20 zoline and 7.8 g. (0.14 mole) of sodiummethoxide in 60 ml. of dimethyl sulfoxide. The solution was stirred atroom temperature for 5 days and poured into 200 ml.

of water. The organic layer was collected in 100 ml. of ether and theether solution was washed with water and dried over magnesium sulfate.The solution was distilled, the fraction boiling at 108 (50 mm.)partially solidified. The solid was collected and recrystallized frompentane to give 3.82 g. (11% yield) of 4-methylamino-2,5,5-tris(trifluoromethyl)-2-difiuoromethyl-3-oxazoline. The H n.m.r. in (CDQ COshowed a triplet (1:53 c.p.s.) at 4.30-r (CF H), a broad singlet at2951- (NH;,), and a doublet (J =4) at 7.351- (CH The F n.m.r. showeddoublets (1:53) split to multiplets at 133.8 p.p.m. (CF H), andmultiplets at 78. 6 p.p.m. (C1 and 74.6 ppm. (2CF Infrared: 2.89 and3.07;; for NH; 3.52pm and 3.38;. for saturated CH; and 6.09, for C=N.

Analysis.-Calcd. for C F H N O: C, 27.13; F, 59.01; H, 1.43; N, 7.91.Found: C, 27.06; F, 58.90; H, 1.41; N, 7.71.

Specific alkyl derivatives of 4-arnin0-3-oxazolines (or their tautomeric4-imino-oxazolidines) in which R and /or Y of the general Formula I arealkyl groups having l-4 carbon atoms, and the reactants from which theyare prepared, as by essentially the procedure of Examples 15 and 16, arelisted in Table III.

TABLE III Reaetants 4-amin0-3-oxazoline (or 4-alkylarnlno-3-oxazollno(or CFzII CFrH plus

TABLE IIICont1nued Reaetants 4-amlno-3-oxazoline (or4-alkylamlno-3-oxazollne (or tautomer) Alkyl halide tautomer) N C z) 2no F l N H C F a i C F 2H C F 2H /OF: NH: HaI F: HN Ha F 2 C F to 0 Fa CF 3 o F 2 o F 2 o C F H 0 F 2H plus C F 2 N CH3 2 t C F: o F t o C F HEXAMPLE 17 Two grams of this freshly distilled isocyanate was4-carbethoxyamino-2-difluoromethyl-2,5 ,5 -tris (tri fluoromethyl-3-oxazo1ine A solution of 15 g. of 4-amino-2-difiuoromethyl-2,5,5-tris(trifiuoromethyl)-3-oxazoline in ml. of oxalyl chloride was heatedto reflux for 2 days, and then distilled under reduced pressure. Therewas obtained 11.21 g. of 4 isocyanato 2 difluoromethyl 2,5,5tris(trifiuoromethyl)-3-oxazoline as a colorless liquid, 13.1. 67 C.

added rapidly to a solution of 1 ml. of ethanol in 50 ml. of diethylether. The reaction mixture was evaporated to dryness under a stream ofnitrogen and the white residue was recrystallized from ether-pentane togive 1.67 g. of 4 carbethoxyamino 2 difluoromethyl 2,5,5 tris(trifluoromethyl)-3-oxazoline as colorless matting needles, M.P. l32133C. The F n.m.r. spectrum in (CD CO showed multiplets at 70.8 p.p.m. (6F)and 76.6 p.p.m. (3F) and a doublet (J :53 c.p.s.) split further tomultiplots at 133.7 p.p.m. from trichlorofluoromethane. The H n.m.r.spectrum showed a broad absorption for NH at -r 0.25; a triplet (1:53c.p.s.) for CF H at 1- 3.64; a quartet (1:7 c.p.s.) for CH at -r 5.72;and a triplet (J=7 c.p.s.) for CH at 1- 8.72.

Analysis.-Calcd. for C H F N O C, 29.14; H, 1.71; F, 50.71; N, 6.77.Found: C, 28.84; H, 1.61; F, 50.88; N, 6.94.

When the process of Example 17 is repeated with the specific4-amino-3-oxazolines listed in the first column of the following TableIV substituted for the starting oxazoline in that example and is firstreacted with oxalyl chloride and the resulting isocyanate then reactedwith the specific alcohols listed in the second column of the table, thespecific urethanes, or carbamates, listed in the third column areformed.

TABLE IV 4- i -3- aollne ofi fig ffii Alcohol Urethane product (ortautomer) CH3O (I) NH: HN 0 OH, 0 F3 c F. I

CF: 0 F3 CH (CH2)aOH NH; HN-JJ O (CHaJsCH; 01cm 01o F2 I ClCFz CFzClC1056i CFzCl O CFzCl C F201 TABLE IV-Contlnued The 4-amino-3-oxalozines,or their tautomers, or alkyl and acyl derivatives thereof of thisinvention are useful for modifying polymers as by lowering the formingtemperatures or pressures or by plasticizing the polymers.

The modification of poly(methyl mcthacrylate) resin is illustrated bythe following experiment:

Example A The following compositions were prepared:

(a) Five-tenths gram of poly(methyl methacrylate) resin containing noadditives.

(b) A mixture of 0.5 g. of poly(methyl methacrylate) resin (molecularweight about 100,000; residual monomer content less than 1%) and 0.1 g.of 4-amino-2,2,5,5- tetrakis(trifluoromethyl)-3-oxazoline.

(c) A mixture of 0.5 g. of poly(methy1 methacrylate) resin and 0.1 g. of4-amino-5-chlorodifluoromethyl-S-difluoromethyl-2,2-bis(trifiuoromethyl)-3-0xaz.oline.

(d) A mixture of 0.5 g. of poly(methyl methacrylate) resin and 0.1 g. of4-dimethy1amin0-2,2,5,5-tetrakis(trifluoromethyl)'3-oxazoline.

(e) A mixture of 0.5 g. of poly(methyl methacrylate) resin and 0.1 g. of4-acetylamino-2,2,5,5-tetrakis(trifluoromethyl)-3-oxazoline.

(f) A mixture of 0.5 g. of poly(methyl methacrylate) resin and 0.1 g. of4amino-2,2,5-tris(difluoromethyl)-5-trifluoromethyl-3-oxazoline.

(g) A mixture of 0.5 g. of poly(methyl methacrylate) resin and 0.1 g. of4-methylamino-2-difiuoro-2,5,S-tris(trifluoromethyl)-3-oxazoline.

(h) A mixture of 0.5 g. of poly(methy1 methacrylate) resin and 0.1 g. of4-amino-6,6,7,7,8,8-hexafiuore-2,2- bis(trifiuoromethyl3-aza-l-oxaspiro[4,31oct-3-ene.

(i) A mixture of 0.5 g. of poly(methyl methacrylate) resin and 0.1 g. of4-amino-2-difluoromethyl-6,6,7,7,8,8- hexafiuoro 2 trifluoromethyl 3 aza1 oxaspiro [4,3]oct-3-ene.

Circular films were pressed from a compact pile of each composition at143 C. and 10,000 lbs. ram pressure for seconds.

The film pressed from composition (a) was 14 mils thick, only 1% inchesin diameter and was incompletely coalesced around the edges.

The film pressed from composition (b) was 9 mils thick and 2% inches indiameter.

The film pressed from composition (c) was 10 mils thick and 2 /8 inchesin diameter.

The film pressed from composition (d) was 8 mils thick and 2% inches indiameter.

The film pressed from composition (e) was 11 thick and 2 /8 inches indiameter.

The film pressed from composition (f) was 10 thick and 2% inches indiameter.

The film pressed from composition (g) was 9 thick and 2% inches indiameter.

The film pressed from composition (h) was 8 thick and 2 /2 inches indiameter.

The film pressed from composition (i) was 8 thick and 2% inches indiameter.

This experiment shows that the forming temperatures or pressures forpoly(methyl methacrylate) resin are lowered by the addition of theoxazolincs of this inventron.

Since obvious modifications and equivalents in the invention will beevident to those skilled in the chemical arts, I propose to be boundsolely by the appended claims.

The embodiments of this invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the group consisting of:

mils

mils

mils

mils

mils

25 wherein:

X and X singly, are alike or diiferent and are selected from the groupconsisting of hydrogen, fluoride and chlorine, or, jointly, areperfluoroalkylene of l to 2 carbons;

X and X are alike or dilferent and are selected from the groupconsisting of hydrogen, fluorine and chlorine;

R is alkyl of 1-4 carbons; and

Y is selected from the group consisting of hydrogen, alkyl of 1-4carbons,

R being alkyl of 1-4 carbons, aryl, alkaryl, or aralkyl of 610 carbonsor substituted aryl, alkaryl or aralkyl of 6-10 carbons, wherein thesubstituents are selected from up to three members of the groupconsisting of fluorine, chlorine and bromine, and R being alkyl orcycloalkyl of up to 10 carbons;

the total number of carbons in R and Y not exceeding 14.

2. The compound of Formula I of claim 1 in which X =X =X =X =F and Y=H,4-arnino, 2,2,S,5-tetrakis (trifluoromethyl)-3-oxazoline.

3. The compound of Formula I of claim 1 in which X =Cl, X =H, X =X =Fand Y=H, 4-amino-2,2-bis (trifiuoromethyl)-5 chlorodifluoromethyl 5difluoromethyl-B-oxazoline.

4. The compound of Formula I of claim 1 in which X =X =X =F, X =Cl andY=H, 4-amino-2-chlorodifluoromethyl-2,5 ,5 -tris trifluoromethyl-3-oxazoline.

5'. The compound of Formula I of claim 1 in which X =X =F, X =X =H andY=H,4amino-2,5-bis(trifluoromethyl)-2,S-bis(difiuoromethyl)-3-oxazoline.

6. The compound of Formula I of claim 1 in which X =X =X =F, X =H andY=H, 4-amino-2,5,5-tris (trifinoromethyl -2-difluoromethyl-3 -oxazoline.

7. The compound of Formula I of claim 1 in which X =X =X =X =F, and

l Y=CH3 4-acetylamino 2,2,5,5 tetrakis(trifluoromethyl) 3 oxazoline.

8. The compound of Formula I of claim 1 in which X and X jointly, are

26 (1) with an alkali metal cyanide, then (2) with an imine of theformula NII x om-ii-cmrr and (3) acidifying the resulting reactionmixture, X X, X and X being as in claim 1.

11. The process of claim 10 carried out in a polar reaction medium.

12. The process of claim 11 in which the polar reaction medium isselected from the group consisting of dimethylformamide, acetonitrile,dimethyl sulfoxide and diethylene glycol dimethyl ether.

13. The process of claim 10 in which the fluoroketone ishexafiuoroacetone.

14. The process of claim 10 in which the fiuoroketone ishexafluoroacetone and the imine is hexafiuoroisopropylidenimine.

15. The process of claim 10 in which the fiuoroketone is 1chloro-l,l,3,3-tetrafluoroacetone and the imine ishexafiuoroisopropylidenimine.

16. The process of claim 10 in which the fiuoroketone ishexafluoroacetone and the imine is chloropentafluoroisopropylidenimine.

17. The process of preparing a compound of Formula I of claim 1 whichcomprises reacting, in the presence of a strongly basic amine,

(1) a polyhaloisopropylidenimine of the formula I IH X- om-o-o F X with(2) a fluoroketone cyanhydrin of the formula X X, X and X being as inclaim 1.

18. The process of claim 17 carried out in a polar reaction medium.

19. The process of claim 18 in which the polar reaction medium isselected from the group consisting of dimethylformamide, acetonitrile,dimethyl sulfoxide and diethylene glycol dimethyl ether.

20. The process of claim 17 in which (1) the polyhaloisopropylidenimineis pentafluoroisopropylidenimine and (2) the fluoroketone cyanhydrin ishexafiuorocyclobutanone cyanhydrin.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

Eichenberger et al., Helv. Chim. Acta, vol. 38, pp. 284- 295 (1955).

ALTON D. ROLLINS, Primary Examiner US. Cl. X.R. 260-304, 464, 465.6,566, 593

a- 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 7,33 Dated June 1, 1971 Inventofls) li m J'- Middleton It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Col. 6, line 59 the whole line should read: "...was bubbled into a.solution of 15 m1 of piperidine and..

Col. 10, line 59 the formula should read: "C7F9H5N2O".

Col. 11, line 16 cancel "infrared".

Col. 12, line 20 correct spelling of "hexafluorocyclobutanone".

Col. 12, line 60 the "on" of the left formula should be "cm".

SigllEFC and sealed this 23rd day of May 1972.

(SEAL) EDWARD I-I.FLEICI IPYR ,JR ROBERT GO'I'TSCHALK Attestlng OfficerCommissioner of Patents

